CN115124067A - For H 2 S detected CuO/WO 3 Method for preparing composite material - Google Patents
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Abstract
A preparation method of a CuO/WO3 composite material for H2S detection belongs to the technical field of metal semiconductor gas sensors. The invention aims to provide a preparation method of a CuO/WO3 composite material for H2S detection, which adopts a simple hydrothermal method to synthesize the CuO/WO3 composite material and can efficiently and accurately detect H2S gas. The invention combines WO 3 Adding the hollow sphere powder into a mixed solution of deionized water and absolute ethyl alcohol, uniformly stirring by using a magnetic stirrer to obtain a yellow solution, and then adding Cu (NO) 3 ) 2 ·3H 2 And O, continuously stirring, adding the mixed solution into a polytetrafluoroethylene high-pressure reaction kettle, transferring the mixed solution into an oven for heating to perform hydrothermal reaction, and automatically performing hydrothermal reaction after the reaction is finishedCooling to room temperature, pouring out the supernatant to obtain precipitate B, centrifuging, collecting the precipitate B, and drying in a constant temperature vacuum drying oven to obtain para-H 2 S gas sensitive CuO/WO 3 The hollow sphere composite material. The invention has high sensitivity, good short-term reproducibility and long-term stability, and good selectivity.
Description
Technical Field
The invention belongs to the technical field of metal semiconductor gas sensors.
Background
Hydrogen sulfide (H) 2 S) is a colorless, highly toxic, flammable acid gas. When the concentration is low, the strong odor of the rotten eggs can cause damage to the central nervous system of a person, and when the concentration is high, the smell of the person can be lost, and the person can even die in a short time. Furthermore, H 2 S is easily dissolved in water to form a strong corrosive acidic solution, which can affect the operation of production equipment and bring about serious economic loss. Thus, H is detected quickly, accurately and economically 2 S gas is vital to human health, industrial production and environmental protection.
In a plurality of H 2 In the S gas detection technology, the metal oxide semiconductor gas sensor is distinguished by the advantages of low cost, quick response, convenience in carrying and the like. The key part of the method is the sensitive material which is currently used for detecting H 2 The S gas metal oxide sensitive material comprises ZnO and WO 3 、SnO 2 、In 2 O 3 CuO, NiO, etc. Among them, WO 3 Is a typical n-type semiconductor, has the forbidden band width of 2.6eV-2.8eV, and has the non-stoichiometric characteristic and high gas-sensitive activity. Therefore, it is widely used in the fields of photocatalysis, photo/electrochromism and gas sensors. Pure WO for the last decade 3 Material for detecting toxic and harmful H 2 WO of different structure, but with good performance on S gas 3 There are some disadvantages such as low response value, high optimum operating temperature, and poor selectivity, and thus, it is necessary to modify them to improve gas sensing performance. Hoa et al synthesized SnO 2 -WO 3 Material pair H 2 S gas detection has the characteristics of high response and low detection limit, which is mainly due to SnO 2 And WO 3 Between which an n-n type heterojunction is formed (Hoa, T.T. N.; Le, D.T. T.; Van Toan, N.; Van Duy, N.; Hung, C. M.; Van Hieu, N.; Hoa, N. D., Highly se)lective H 2 S gas sensor based on WO 3 -coated SnO 2 nanowires. Materials Today Communications 2021,26, 102094.). Xiao et al reported WO having a porous face-centered cubic structure 3 The specific structure of the material can increase the specific surface area and the porosity of the material. Furthermore, WO 3 the/NiO material reacts with H at the working temperature of 250 DEG C 2 Production of WS during S reaction 2 NiS intermediate product, air-sensitive Performance is obviously improved (Xiao, X.; Zhou, X.; Ma J.; Zhu, Y.; Cheng, X.; Luo, W.; Deng, Y.; radial Synthesis and Gas Sensing Performance of Ordered Mesoporous semiconductor WO) 3 /NiO Composites. ACS applied materials & interfaces 2019,11(29), 26268-26276.). Therefore, many research works in recent years mainly focus on both improving the material morphology and building heterojunctions.
WO can be found in the investigation of the current research situation at home and abroad 3 As H 2 The S gas sensor sensitive material has made great progress, but still has the defects of high manufacturing cost, high working temperature, poor short-term reproducibility and long-term stability, poor selectivity and the like, cannot meet the current actual use requirements, and limits the large-scale production and application of the S gas sensor sensitive material.
Disclosure of Invention
The invention aims to provide a preparation method of a CuO/WO3 composite material for H2S detection, which adopts a simple hydrothermal method to synthesize a CuO/WO3 composite material and can efficiently and accurately detect H2S gas.
The method comprises the following steps:
(1) WO (International patent application) 3 Weighing 0.15-0.25 g of hollow sphere powder, adding the powder into a mixed solution of deionized water and absolute ethyl alcohol, and uniformly stirring the solution by using a magnetic stirrer to obtain a yellow solution; the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 1, magnetically stirring for 25-35 min;
(2) then adding 0.03-0.04 g Cu (NO) into the yellow solution 3 ) 2 ·3H 2 Continuously stirring to uniformly mix the solution; stirring for 50-70 min, wherein the molar ratio of W to Cu is 6: 1;
(3) adding the mixed solution into a 50 mL polytetrafluoroethylene high-pressure reaction kettle, and transferring the mixed solution into an oven for heating to perform hydrothermal reaction; the temperature of the oven is set to be 170-190 ℃, and the reaction time is 4-6 h;
(4) naturally cooling to room temperature after the reaction is finished, pouring out the supernatant to obtain a precipitate B, centrifugally collecting, and washing with deionized water and absolute ethyl alcohol for several times respectively until the supernatant is clear and transparent; the centrifugal rotating speed is 2000-4000 r/min, the centrifugal washing is carried out for 6-7 times, the first 3-4 times of washing is carried out by deionized water, and the second 3-4 times of washing is carried out by absolute ethyl alcohol;
(5) putting the obtained precipitate B into a constant-temperature vacuum drying oven for drying for 8-12H to obtain p-H 2 S gas sensitive CuO/WO 3 A hollow sphere composite material; the temperature of the constant-temperature vacuum drying box is generally set to be 60-70 ℃, the vacuum degree is maintained at 800 Pa under 700-.
CuO/WO according to the invention 3 The hollow sphere composite material has the structural form that: CuO/WO 3 Hollow sphere form namely CuO composite WO 3 The diameter of the hollow sphere is 1.2-1.4 mu m, and the CuO formed by a copper source is loaded on WO 3 The surface of the sphere is rough, loose and porous.
CuO/WO according to the invention 3 The preparation method of the gas sensitive material of the gas sensor comprises the following steps: mixing CuO/WO 3 Coating the hollow ball material on the surface of the ceramic tube, and manufacturing a gas-sensitive sensor element, wherein the gas-sensitive sensor element consists of the ceramic tube, a platinum wire, a gold electrode, a heating wire and a sensitive layer; firstly, mixing a small amount of synthetic material and deionized water to form slurry, then dipping the slurry by using a brush pen, uniformly coating the slurry on the surface of the cleaned ceramic tube, air-drying the ceramic tube for 30 minutes at room temperature, then inserting the ceramic tube into a nichrome heater for aging for 3 days to enhance the stability of the ceramic tube, and placing the prepared gas sensitive element into a gas chamber for gas sensitive performance test.
The invention uses CuO/WO 3 CuO/WO prepared by taking hollow sphere composite material as main material 3 Gas sensor detection H 2 The S gas response value performance is improved, and 0.1 to 50ppm H is continuously and circularly detected 2 And (4) S gas.
The invention has high sensitivity, good short-term reproducibility and long-term stability, good selectivity and the following advantages and beneficial effects:
1. preparation of hollow ball CuO/WO with hierarchical structure by simple two-step hydrothermal method 3 The sensor does not need any surfactant or template, has low manufacturing cost and simple operation, and can realize large-scale production and practical application.
2.CuO/WO 3 Composite material for 10ppm H 2 The response of S was 1297, vs. WO 3 The response is approximately 103 times higher. It is 56.3% higher than the optimal 10ppm response (830) reported in the literature for this material to date.
3. Detection of H at Low temperatures (70 ℃ C.) due to sulfurization of CuO and the presence of a p-n heterojunction 2 S gas has a high response signal.
4.CuO/WO 3 The sensor can be used for H of 0.1-50 ppm 2 S is used for continuous circulating gas detection, short-term reproducibility and long-term stability are good, and the lower limit of detection is as low as 100 ppb.
Drawings
FIG. 1 is a scheme for preparing CuO/WO according to the present invention 3 Materials and WO 3 XRD spectrum of the material;
FIG. 2 is a scheme for preparing CuO/WO according to the present invention 3 Materials and WO 3 SEM spectra of the material;
FIG. 3 is a process for preparing CuO/WO according to the present invention 3 A TEM spectrum of the material;
FIG. 4 is a process for preparing CuO/WO according to the present invention 3 Materials and WO 3 Material gas sensor pair 10ppm H 2 S and the optimal working temperature;
FIG. 5 is a process for preparing CuO/WO according to the present invention 3 Materials and WO 3 Pair of materials 10ppm H 2 S gas response recovery curve graph;
FIG. 6a is a process for preparing CuO/WO according to the present invention 3 1-50-1 ppmH at 70 ℃ for material sensor 2 S, dynamic sensing characteristics;
FIG. 6b is a schematic diagram of the present invention for preparing CuO/WO 3 1-50 ppm H at 70 deg.C of material sensor 2 Response value of S gas
FIG. 6c is a schematic diagram of the preparation of CuO/WO according to the present invention 3 Material sensor at 70 deg.C for 5-0.1 ppmH 2 The response curve of S (the inset is the raw data);
FIG. 7 is a process for preparing CuO/WO according to the present invention 3 Materials and WO 3 A selectivity test pattern of the material to different gases;
FIG. 8a is a process for preparing CuO/WO according to the present invention 3 Exposure of the Material sensor to 10ppm H at 70 deg.C 2 In S, a sensitivity curve graph obtained by 10 response/desorption experiments is carried out on the 10 th day;
FIG. 8b is a schematic diagram of the present invention for preparing CuO/WO 3 Exposure of the Material sensor to 10ppm H at 70 deg.C 2 S, a sensitivity curve graph obtained by carrying out 14 response/desorption experiments on the 26 th day;
FIG. 8c is a schematic diagram of the preparation of CuO/WO according to the present invention 3 Materials and WO 3 Material sensor pair 10ppm H 2 Long-term stability (70 ℃) test curve for S.
Detailed Description
The invention utilizes a hydrothermal method to synthesize a precursor and then calcines the precursor to obtain WO 3 The material is then introduced with a copper source to synthesize CuO nano-particle composite WO 3 A hollow microsphere material. With pure WO 3 In contrast, CuO/WO 3 The gas sensing performance of the sensor is obviously improved, and the gas sensor can detect 10ppm H at the optimal working temperature of 70 DEG C 2 The response value of S is as high as 1297, which is about pure WO 3 103 times higher. Furthermore, CuO/WO 3 The sensor can be used for H of 0.1-50 ppm 2 And S is used for continuous circulating gas detection, and the reproducibility is good. The preparation process is simple, the cost is low, any surfactant and template agent are not added, the green chemical development concept is met, and meanwhile, the material gas sensor is used for H 2 The sensitivity and selectivity of S are far higher than those of other metal oxides, and the method has great production and application prospects in the field of gas sensors.
CuO/WO prepared by the invention 3 Composite material sensor improvement pair H 2 The detection of S gas is mainly summarized as the following three aspects: first, CuO nanoparticles are dispersively grown in WO 3 The surface of the hollow sphere not only prevents the aggregation of CuO particles but also ensures thatThe surface of the material is rougher. This structure increases the specific surface area and effective adsorption sites and also provides more transport channels for gas diffusion. Second, CuO and WO 3 Have different fermi levels and form a p-n heterostructure and a specific electron donor-acceptor system when interacting. Electrons are transferred between the two metals, the energy band is bent, the electron transmission is accelerated, and the depletion layer becomes thick. Finally, CuO is preferentially associated with H 2 The S gas reacts to form CuS with metal characteristics, the p-n junction is damaged, and the conductivity is obviously improved. Researches show that the gas-sensitive material has excellent gas-sensitive properties such as low working temperature, good selectivity, high sensitivity and the like.
The present invention is described in further detail below:
1. the preparation method is simple (hydrothermal method),
(1) 0.3-0.5 g of WCl 6 Adding into 30-40 mL glacial acetic acid, stirring with a magnetic stirrer, and changing the solution from black brown to blue;
(2) pouring the mixed solution into a 50 mL high-pressure reaction kettle with polytetrafluoroethylene as an inner liner, and putting the high-pressure reaction kettle into an oven for hydrothermal reaction;
(3) naturally cooling to room temperature after the reaction is finished, pouring out the supernatant, centrifugally collecting the precipitate A, and centrifugally washing with deionized water and absolute ethyl alcohol for several times respectively until the supernatant is clear and transparent;
(4) putting the obtained precipitate A into a constant-temperature vacuum drying oven for drying for 8-12H, and then calcining in a muffle furnace to obtain a pair H 2 S gas sensitive WO 3 Hollow sphere powder, as a control group;
(5) the WO obtained in the step (4) is 3 Weighing 0.15-0.25 g of the mixture, adding the mixture into a mixed solution of deionized water and absolute ethyl alcohol, and uniformly stirring the mixture by using a magnetic stirrer to obtain a yellow solution;
(6) then adding 0.03-0.04 g Cu (NO) into the yellow solution 3 ) 2 ·3H 2 Continuously stirring to uniformly mix the solution;
(7) adding the mixed solution into a 50 mL polytetrafluoroethylene high-pressure reaction kettle, and transferring the mixed solution to an oven for heating to perform hydrothermal reaction;
(8) naturally cooling to room temperature after the reaction is finished, pouring out the supernatant, centrifugally collecting the precipitate B, and washing with deionized water and absolute ethyl alcohol for several times respectively until the supernatant is clear and transparent;
(9) putting the obtained precipitate B into a constant-temperature vacuum drying oven for drying for 8-12H to obtain p-H 2 S gas sensitive CuO/WO 3 The hollow sphere composite material is taken as an experimental group;
in the step (1), the magnetic stirring time is 25-35 min.
The temperature of the oven in the step (2) is set to be 170-190 ℃, and the reaction time is 11-13 h.
In the step (3), the centrifugal rotating speed is 2000-4000 r/min, the centrifugal washing is carried out for 6-7 times, the first 3-4 times of washing is carried out by using the deionized water, and the second 3-4 times of washing is carried out by using the absolute ethyl alcohol.
The temperature of the constant-temperature vacuum drying box in the step (4) is generally set to be 60-70 ℃, the vacuum degree is maintained at 800 Pa under 700-.
In the step (5), the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 1, magnetically stirring for 25-35 min.
In the step (6), the stirring time is 50-70 min, and the molar ratio of W to Cu is 6: 1.
the temperature of the oven in the step (7) of the invention is set as 170-190 ℃, and the reaction time is 4-6 h.
In the step (8), the centrifugal rotating speed is 2000-4000 r/min, the centrifugal washing is carried out for 6-7 times, the first 3-4 times of washing is carried out by using the deionized water, and the second 3-4 times of washing is carried out by using the absolute ethyl alcohol.
The temperature of the constant-temperature vacuum drying oven in the step (9) of the invention is generally set to be 60-70 ℃, and the vacuum degree is kept at 800 Pa and 700 ℃.
2. Vacuum microsphere:
the material was scanned using an x-ray powder diffractometer (XRD-7000, MAXIMaCo. Ltd., Japan) and the crystal structure was analyzed at a scanning speed of 8 min -1 The scanning range is 10-80 degrees. Using electric field hairThe morphological structure of the samples was characterized by transmission electron microscopy (SEM, FEI aspect F50) and transmission electron microscopy (TEM, FEI Tecnai G2F 20).
The gas sensing process of metal oxides is usually performed at the surface thereof. Therefore, the surface topography of the material is closely related to the performance of the sensor. FIG. 1 shows CuO/WO prepared in this example 3 The XRD spectrum of the hollow microsphere shows that the diffraction peaks with similar characteristics can be seen from the graph and the monoclinic WO 3 The standard maps of (JCPDS No. 72-0677) are consistent, and the purity of the synthesized sample is proved to be high. Diffraction peaks at 23.109 °, 23.579 °, 24.349 °, 33.252 °, 34.151 °, 49.893 ° and 55.894 °, respectively corresponding to monoclinic WO 3 The (002), (020), (200), (022), (202), (400) and (420) crystal planes of (a). Furthermore, CuO/WO 3 The sample was almost identical to pure WO 3 There was no significant difference in the diffraction peaks of (a) indicating that there was no change in the crystallinity of the sample, which is probably due to the small grain size of the CuO nanoparticles in WO 3 High dispersion of the surface. However, it can be found carefully that around 35.50 °, the intensity of the peak is increased, since the diffraction peaks of 35.465 ° and 35.565 ° correspond to the (002) and (-111) crystal planes of monoclinic CuO, respectively (JCPDS No. 80-1268).
WO part a from FIG. 2 3 From SEM images of different magnifications, WO 3 The sample is in a hollow sphere shape, the diameter is 0.9-1.1 mu m, no other forms exist, and the surface of the sample is rough. At the same time, WO can be clearly seen 3 Is a three-dimensional spherical structure self-assembled by a plurality of one-dimensional nano particles. In figure 2, part b is CuO composite WO 3 The diameter of the hollow sphere is 1.2-1.4 mu m, and the sphere is enlarged, because the CuO formed after the copper source is introduced is loaded on WO 3 The surface of the sphere is maintained, but the original WO is still maintained 3 The surface becomes rough due to the hollow sphere structure. Furthermore, sample CuO/WO 3 Is compared with WO 3 The surface of the hollow sphere is more loose and porous, and the formation of pores is promoted due to the solvothermal reaction at high temperature and the low-temperature drying. The formation of voids is primarily a result of stress relief and structural mismatch. In one aspect, the CuO/WO is prepared solvothermally 3 The precursor is inReleasing stress by forming pores in the high-temperature high-pressure reaction process so as to prevent structural damage in the crystal growth process; on the other hand, CuO/WO 3 Precursor and hydrate mismatch promotes pore formation. The special surface structure increases the surface defects of the hollow microspheres and provides more oxygen vacancies and adsorption sites for the test gas.
Portions a and b of FIG. 3 show CuO/WO 3 TEM analysis of the hollow microspheres. By comparing the graph to concentrate the bright field and the dark field, the existence of the hollow sphere structure can be clearly observed, the structure can provide a channel for gas transmission, also can improve the kinetic factor of gas diffusion, and is beneficial to CuO/WO 3 And the gas-sensitive performance is improved. Further, the existence of CuO nanoparticles and the coexistence of multiple lattices can be seen from the gray-labeled points in the figure, which are CuO and WO 3 Coexistence and successful construction of p-n heterojunctions.
3. Detection of H 2 The S gas response value performance is improved, and 0.1 to 50ppm H can be continuously and circularly detected 2 S gas
With WO 3 As a control, CuO/WO 3 For the experimental group, assay H was performed 2 And S, testing and analyzing gas-sensitive performance.
The operating temperature has a great influence on the contact reaction between the gas and the sensitive material, which is closely related to the gas sensitive properties of the sensor. FIG. 4 shows the sensor pair 10ppm H 2 The response value of the S gas is related to the working temperature. During the gas sensitive test, the response curve of the sensor shows the same trend of "increase-max-decay". The sensor showed the greatest response at 70 ℃, which is probably due to the response to H at the optimum temperature 2 Efficient adsorption of S molecules and the highest chemical reactivity of the sensing layer. Therefore, in the following tests, 70 ℃ was chosen as the optimum operating temperature. WO 3 And CuO/WO 3 Sensor pair 10ppm H 2 The response values (Ra/Rg) of S were 12.50 and 1297, respectively. It can be seen that the surface of the CuO nanoparticles is modified with WO 3 The response value of the hollow microsphere sensor is obviously improved. About pure WO 3 103 times that of the sensor.
The response/recovery capability plays an important role in characterizing the gas-sensitive properties of the material. Part a and part b of FIG. 5 are WO 3 Sensor and CuO/WO 3 Sensor for 10ppm H at 70 deg.C 2 Response-desorption curve of S. CuO/WO 3 The composite significantly improved response time, from 48 s to 13 s (as in Table 1), which is probably due to H 2 The S gas can preferentially react with the CuO nano-particles loaded on the surface to generate a CuS intermediate product, so that the quick response of the sensor is promoted. After the reaction is finished, the target gas is transferred to the air, and the energy resolving and absorbing capacity is weak at low working temperature, and the natural recovery time is long, so that a short-time pulse current needs to be provided outside the sensor to accelerate H 2 The S molecules are separated from the CuO surface. WO 3 And CuO/WO 3 Heating at 200 deg.C and 120 deg.C for 76 s respectively.
FIG. 6a shows CuO/WO 3 Sensor for different concentrations of H at 70 deg.C 2 Dynamic response curve of S gas. The whole test process is at H 2 The concentration of S gas is continuously changed from 1ppm to 50ppm to 1 ppm. When exposed to different concentrations of H 2 In S gas, CuO/WO 3 The sensor makes a rapid and distinct response, and as the gas concentration increases, the magnitude of the response increases. Furthermore, in the cyclic dynamic test, CuO/WO 3 Sensor H at different concentrations 2 S gas has almost the same corresponding concentration response value, which shows good reproducibility, FIG. 6b is a diagram of the preparation of CuO/WO according to the present invention 3 1-50 ppm H at 70 deg.C of material sensor 2 Response value of S gas. FIG. 6c shows CuO/WO 3 For 0.1-5ppm of H at 70 DEG C 2 Response curve of S concentration with minimum detection lower limit of 100ppb of H 2 S, the response value is 2.34. .
Selectivity is another key indicator of gas sensors. In WO 3 And CuO/WO 3 In the selectivity experiment, the sensors were exposed to 10ppm of H, respectively 2 S gas, 100ppm SO 2 、NO 2 CO and 1000 ppm ethanol, methanol, ethylene glycol, acetone, as shown in figure 7. The results show that WO at the optimum operating temperature 3 And CuO/WO 3 Sensor pair H 2 The response value of S gas is significantly higher than other gases. With WO 3 In contrast, CuO/WO 3 Sensor pair H under the same conditions 2 The S gas response value is higher. This result indicates that CuO/WO is present 3 Is very suitable for carrying out H at low temperature (70 ℃) 2 And S gas detection. Enhanced CuO/WO 3 Sensor in H 2 The selectivity in S detection has important significance for practical application.
Short-term reproducibility and long-term stability are crucial for practical application of MOS sensors. We tested CuO/WO 3 Short-term reproducibility of the sensor (FIGS. 8a, 8 b) and WO 3 With CuO/WO 3 Long term stability of the sensor (fig. 8 c) gas sensitive response curve. FIGS. 8a and 8b are CuO/WO 3 Sensor exposure to 10ppm H at optimum operating temperature 2 S, sensitivity profiles obtained by 10 and 14 response/desorption experiments on the 10 th and 26 th days, respectively. It is clear from the above that the sensor shows good response/desorption performance at the optimum working temperature, and has better reproducibility. In CuO/WO 3 In the long-term stability test of the sensor, CuO/WO 3 The sensor has the negligible response value reduction phenomenon in 30 days, the whole curve basically keeps stable, and the long-term stability is better. The negligible degradation of the response may be due to CuO/WO 3 Reduction of surface active sites and H 2 S gas can not be completely desorbed from the surface of the material, and partial formed substances such as CuS and the like. Nevertheless, CuO/WO 3 The response value of the sensor is still higher than that of pure WO 3 The sensor is much taller.
TABLE 1 WO 3 Base material detection H 2 S gas
The present invention is in CuO/WO 3 In the design, synthesis and test of the sensor, the graded hollow spherical WO is respectively synthesized by a hydrothermal method 3 And CuO/WO 3 Composite material and use for detecting H 2 And (4) S gas. By using the methodThe method synthesizes CuO NPs which are dispersedly grown in WO 3 On the surface, a large number of reaction active sites are introduced, and a p-n heterojunction is successfully constructed. Exposure to 10ppm H 2 And S, the ultra-high response value of 1297 (Ra/Rg) and the ultra-fast response speed of 13S are realized at the low temperature of 70 ℃. Furthermore, CuO/WO 3 The selectivity, reproducibility and long-term stability of (1: 6) were all good. Thus, hollow spheres WO modified with CuO nanoparticles 3 The sensor is used for realizing low-temperature and high-efficiency detection of H 2 S gas provides a strategy and has great practical application potential.
CuO/WO according to the invention 3 The specific method for preparing the gas sensor comprises the following steps:
the gas sensor element consists of a ceramic tube, a platinum wire, a gold electrode, a heating wire and a sensitive layer. Firstly, a small amount of synthetic material is mixed with deionized water to form slurry, and then the slurry is dipped by a brush pen and is uniformly coated on the surface of the cleaned ceramic tube. After air-drying at room temperature for 30 minutes, it was aged (3 days) in a nichrome heater to enhance its stability. And placing the prepared gas sensor into a gas chamber for gas-sensitive performance test.
Detection of H 2 S gas CuO/WO 3 The preparation method of the gas-sensitive material of the gas sensor is characterized in that CuO/WO is added 3 The hollow ball material is coated on the surface of the ceramic tube to manufacture the gas sensor element, and the method specifically comprises the following steps:
the gas sensor element consists of a ceramic tube, a platinum wire, a gold electrode, a heating wire and a sensitive layer. Firstly, a small amount of synthetic material is mixed with deionized water to form slurry, and then the slurry is dipped by a brush pen and is uniformly coated on the surface of the cleaned ceramic tube. After air-drying at room temperature for 30 minutes, the plates were aged (3 days) in a nichrome heater to enhance their stability. And placing the prepared gas sensor into a gas chamber for gas-sensitive performance test.
Example 1
(1) 0.3g of WCl 6 Adding into 30 mL glacial acetic acid, stirring with magnetic stirrer for 30 min to change the solution from black brown to blue;
(2) pouring the mixed solution into a 50 mL high-pressure reaction kettle with polytetrafluoroethylene as a lining, and putting the high-pressure reaction kettle into a drying oven for hydrothermal reaction at the reaction temperature of 170 ℃ for 12 hours;
(3) naturally cooling to room temperature after the reaction is finished, pouring out the supernatant, centrifugally collecting the precipitate A, and centrifugally washing the precipitate A for 3 times by using deionized water and centrifugally washing the precipitate A for 3 times by using absolute ethyl alcohol respectively until the supernatant is clear and transparent;
(4) putting the obtained precipitate A into a constant-temperature vacuum drying oven at 60 ℃ for drying for 8H, then calcining in a muffle furnace, taking air as background gas, raising the temperature to 490 ℃ at the temperature rise rate of 2 ℃/min, wherein the calcining time is 1H, and obtaining the p-H 2 S gas sensitive WO 3 Hollow sphere powder;
(5) the WO obtained in the step (4) is 3 Weighing 0.15 g of the mixture, adding the mixture into 30 mL of deionized water and absolute ethyl alcohol mixed solution (the volume ratio is 1: 1), and stirring the mixture for 30 min by using a magnetic stirrer to obtain yellow solution;
(6) thereafter, 0.03 g of Cu (NO) was added to the yellow solution 3 ) 2 ·3H 2 Continuously stirring for 1 hour to uniformly mix the solution;
(7) adding the mixed solution into a 50 mL polytetrafluoroethylene high-pressure reaction kettle, transferring the mixed solution into an oven, and heating the mixed solution to perform oxidation-reduction reaction at the reaction temperature of 170 ℃ for 5 hours;
(8) naturally cooling to room temperature after the reaction is finished, pouring out the supernatant, centrifugally collecting the precipitate B, and centrifugally washing the precipitate B for 3 times by using deionized water and centrifugally washing the precipitate B for 3 times by using absolute ethyl alcohol respectively until the supernatant is clear and transparent;
(9) putting the obtained precipitate B into a constant-temperature vacuum drying oven at 60 ℃ for drying for 8H to obtain p-H 2 S gas sensitive CuO/WO 3 A hollow sphere composite material;
(10) 0.03 g of the synthetic material was mixed with deionized water to prepare a slurry, and the slurry was dipped with a brush pen and uniformly coated on the surface of the cleaned ceramic tube. After air-drying at room temperature for 30 minutes, it was aged (3 days) in a nichrome heater to enhance its stability. And placing the prepared gas sensor into a gas chamber for gas-sensitive performance test.
Example 2
(1) 0.5 g of WCl 6 Adding into 40 mL glacial acetic acid, stirring with a magnetic stirrer for 30 min, and changing the solution from black brown to blue;
(2) pouring the mixed solution into a 50 mL high-pressure reaction kettle with polytetrafluoroethylene as a lining, and putting the high-pressure reaction kettle into a drying oven for hydrothermal reaction at the reaction temperature of 190 ℃ for 12 hours;
(3) naturally cooling to room temperature after the reaction is finished, pouring out the supernatant, centrifugally collecting the precipitate A, and respectively centrifugally washing the precipitate A for 4 times by using deionized water and 3 times by using absolute ethyl alcohol until the supernatant is clear and transparent;
(4) putting the obtained precipitate A into a constant-temperature vacuum drying oven at 60 ℃ for drying for 10H, then calcining in a muffle furnace, taking air as background gas, raising the temperature to 510 ℃ at the temperature rise rate of 2 ℃/min, wherein the calcining time is 1H, and obtaining the p-H 2 S gas sensitive WO 3 Hollow sphere powder;
(5) the WO obtained in the step (4) is 3 Weighing 0.25 g of the mixture, adding the mixture into 30 mL of a mixed solution of deionized water and absolute ethyl alcohol (the volume ratio is 1: 1), and stirring the mixture for 30 min by using a magnetic stirrer to obtain a yellow solution;
(6) thereafter, 0.04 g of Cu (NO) was added to the yellow solution 3 ) 2 ·3H 2 Continuously stirring for 1 hour to uniformly mix the solution;
(7) adding the mixed solution into a 50 mL polytetrafluoroethylene high-pressure reaction kettle, transferring the mixed solution into an oven, and heating the mixed solution to perform oxidation-reduction reaction at 190 ℃ for 5 hours;
(8) naturally cooling to room temperature after the reaction is finished, pouring out the supernatant, centrifugally collecting the precipitate B, and centrifugally washing the precipitate B for 4 times by using deionized water and centrifugally washing the precipitate B for 3 times by using absolute ethyl alcohol respectively until the supernatant is clear and transparent;
(9) putting the obtained precipitate B into a constant-temperature vacuum drying oven at 60 ℃ for drying for 10H to obtain p-H 2 S gas sensitive CuO/WO 3 A hollow sphere composite material;
(10) 0.03 g of the synthetic material was mixed with deionized water to prepare a slurry, and the slurry was dipped with a brush pen and uniformly coated on the surface of the cleaned ceramic tube. After air-drying at room temperature for 30 minutes, the plates were aged (3 days) in a nichrome heater to enhance their stability. And placing the prepared gas sensor into a gas chamber for gas-sensitive performance test.
Example 3
(1) 0.4 g of WCl 6 Adding into 35 mL glacial acetic acid, stirring with a magnetic stirrer for 30 min, and changing the solution from black brown to blue;
(2) pouring the mixed solution into a 50 mL high-pressure reaction kettle with polytetrafluoroethylene as a lining, and putting the reaction kettle into a drying oven for hydrothermal reaction at the reaction temperature of 180 ℃ for 12 hours;
(3) naturally cooling to room temperature after the reaction is finished, pouring out the supernatant, centrifugally collecting the precipitate A, and centrifugally washing the precipitate A for 4 times by using deionized water and centrifugally washing the precipitate A for 4 times by using absolute ethyl alcohol respectively until the supernatant is clear and transparent;
(4) putting the obtained precipitate A into a constant-temperature vacuum drying oven at 70 ℃ for drying for 12H, then calcining in a muffle furnace, taking air as background gas, raising the temperature to 500 ℃ at the temperature rise rate of 2 ℃/min, wherein the calcining time is 1H, and obtaining the p-H 2 S gas sensitive WO 3 Hollow sphere powder;
(5) the WO obtained in the step (4) is 3 Weighing 0.2 g of the mixture, adding the mixture into 30 mL of a mixed solution of deionized water and absolute ethyl alcohol (the volume ratio is 1: 1), and stirring the mixture for 30 min by using a magnetic stirrer to obtain a yellow solution;
(6) then 0.035 g Cu (NO) was added to the yellow solution 3 ) 2 ·3H 2 Continuously stirring for 1 hour to uniformly mix the solution;
(7) adding the mixed solution into a 50 mL polytetrafluoroethylene high-pressure reaction kettle, transferring the mixed solution into an oven, and heating the mixed solution to perform oxidation-reduction reaction at the reaction temperature of 180 ℃ for 5 hours;
(8) naturally cooling to room temperature after the reaction is finished, pouring out the supernatant, centrifugally collecting the precipitate B, and centrifugally washing the precipitate B for 4 times by using deionized water and centrifugally washing the precipitate B for 4 times by using absolute ethyl alcohol respectively until the supernatant is clear and transparent;
(9) putting the obtained precipitate B into a constant-temperature vacuum drying oven at 70 ℃ for drying for 12H to obtain p-H 2 S gas sensitive CuO/WO 3 A hollow sphere composite material;
(10) 0.03 g of the synthetic material was mixed with deionized water to prepare a slurry, and the slurry was dipped with a brush pen and uniformly coated on the surface of the cleaned ceramic tube. After air-drying at room temperature for 30 minutes, the plates were aged (3 days) in a nichrome heater to enhance their stability. And placing the prepared gas sensor into a gas chamber for gas-sensitive performance test.
Claims (4)
1. A preparation method of a CuO/WO3 composite material for H2S detection is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing WO 3 Weighing 0.15-0.25 g of hollow sphere powder, adding the powder into a mixed solution of deionized water and absolute ethyl alcohol, and uniformly stirring the solution by using a magnetic stirrer to obtain a yellow solution; the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 1, magnetically stirring for 25-35 min;
(2) then adding 0.03-0.04 g Cu (NO) into the yellow solution 3 ) 2 ·3H 2 Continuously stirring to uniformly mix the solution; stirring for 50-70 min, wherein the molar ratio of W to Cu is 6: 1;
(3) adding the mixed solution into a 50 mL polytetrafluoroethylene high-pressure reaction kettle, and transferring the mixed solution into an oven for heating to perform hydrothermal reaction; the temperature of the oven is set to be 170-190 ℃, and the reaction time is 4-6 h;
(4) naturally cooling to room temperature after the reaction is finished, pouring out the supernatant to obtain a precipitate B, centrifugally collecting, and washing with deionized water and absolute ethyl alcohol for several times respectively until the supernatant is clear and transparent; the centrifugal rotating speed is 2000-4000 r/min, the centrifugal washing is carried out for 6-7 times, the first 3-4 times of washing is carried out by deionized water, and the second 3-4 times of washing is carried out by absolute ethyl alcohol;
(5) putting the obtained precipitate B into a constant-temperature vacuum drying oven for drying for 8-12H to obtain p-H 2 S gas sensitive CuO/WO 3 Hollow ball complexCombining materials; the temperature of the constant-temperature vacuum drying box is generally set to be 60-70 ℃, the vacuum degree is maintained at 800 Pa under 700-.
2. The method for preparing a CuO/WO3 composite material for H2S detection as claimed in claim 1, wherein the method comprises the following steps: CuO/WO 3 The hollow sphere composite material has the structural form that: CuO/WO 3 Hollow sphere form namely CuO composite WO 3 The diameter of the hollow sphere is 1.2-1.4 mu m, and the CuO formed by a copper source is loaded on WO 3 The surface of the sphere is rough, loose and porous.
3. The method for preparing a CuO/WO3 composite material for H2S detection as claimed in claim 1, wherein the method comprises the following steps: CuO/WO 3 The preparation method of the gas sensitive material of the gas sensor comprises the following steps: mixing CuO/WO 3 Coating the hollow ball material on the surface of the ceramic tube, and manufacturing a gas-sensitive sensor element, wherein the gas-sensitive sensor element consists of the ceramic tube, a platinum wire, a gold electrode, a heating wire and a sensitive layer; firstly, mixing a small amount of synthetic material with deionized water to form slurry, dipping the slurry by using a writing brush, uniformly coating the slurry on the surface of the cleaned ceramic tube, air-drying the ceramic tube for 30 minutes at room temperature, then inserting the ceramic tube into a nickel-chromium alloy heater for aging for 3 days to enhance the stability of the ceramic tube, and placing the prepared gas sensitive element into a gas chamber for gas sensitive performance test.
4. The preparation method of the CuO/WO3 composite material for H2S detection as claimed in claim 1 or 3, wherein: with CuO/WO 3 CuO/WO prepared by taking hollow sphere composite material as main material 3 Gas sensor detection H 2 The S gas response value performance is improved, and the continuous cycle detection is carried out for 0.1 to 50ppm H 2 And (4) S gas.
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